Addition of coupling agent during organolithium initiated polymerizations

ABSTRACT

Continuous or incremental addition of a coupling agent, such as silicon tetrachloride, during the polymerization step of organolithium initiated polymerization processes results in polymers of improved processability, as well as other improved properties such as high green strength, low die swell, and minimal shrinkage on extrusion.

This is a divisional application of Ser. No. 447,203 filed Mar. 1, 1974,now U.S. Pat. No. 4,020,258, issued Apr. 26, 1977 which is acontinuation application of Ser. No. 195,810 filed Nov. 4, 1971, nowabandoned.

FIELD OF THE INVENTION

This invention relates to the preparation of conjugated diene polymers.

In another aspect, the invention relates to a manner of modifying apolymerization process utilizing organolithium initiators.

BACKGROUND OF THE INVENTION

Numerous studies have been made in an effort to improve theprocessability of the broad class of polymers of conjugated dienes,particularly the solution polymerized polymers. In general, a broadermolecular weight distribution is desired in polymers of conjugateddienes including homopolymers of conjugated dienes, copolymers ofconjugated dienes, and copolymers of conjugated dienes withmonovinyl-substituted aromatic compounds. Polymers of broader molecularweight distribution tend to have more desirable processingcharacteristics such as better banding on a roll mill, faster and bettermixing of compound recipes in an internal mixer, reduced cold flow, ascompared to polymers with relatively narrow molecular weightdistribution. Improved processability characteristics ofsolution-polymerized polymers are desired so as to be equivalent to theprocessability of the emulsion-polymerized polymers. Theemulsion-polymerized polymers are more difficult and expensive to make.Improving the properties of the more easily and economically preparedsolution-polymerized polymers would improve the competitive position ofthe latter.

SUMMARY OF THE INVENTION

The continuous or incremental additions of nonpolymerizable couplingagents, such as of the silicon tetrahalides and the like, during atleast a portion of the course of the polymerization step ofpolymerizations after initiation with organolithium initiators resultsin polymeric products of much improved processability characteristics ascompared to similar polymers made by conventional methods. My inventionis applicable to polymerization of monomers which are polymerizable withorganolithium initiators.

The improved polymers not only provide better milling of the rubberypolymers, but the polymers produced according to my invention alsoexhibit significantly high and desirable green strength, low die swell,low shrinkage on extrusion, all characteristics quite valuable inrubbery product utilizations. Another characteristic of polymers of myinvention are the generally low viscosities of solutions of polymers ofconjugated dienes in hydrocarbons such as styrene. These solutions areuseful in the manufacture of high impact polystyrene, and low solutionviscosity is an advantage in the manufacture thereof.

DETAILED DESCRIPTION OF THE INVENTION Coupling Agents

My invention is broadly concerned with what I term the essentiallycontinuous addition of non-polymerizable coupling agents during at leasta portion of the polymerization of the monomer or monomers in thepolymerization system, commencing after polymerization of the monomershas been initiated in the polymerization system. The term "essentiallycontinuous" is intended to include incremental addition or the additionof discrete portions of the non-polymerizable coupling agent separatedby discrete intervals of time. Suitable coupling reagents are thosewhich can be broadly termed the non-polymerizable coupling agents.

Suitable agents can be represented by the general formula R_(a) MZ_(b)in which R is a hydrocarbyl radical, preferably alkyl, cycloalkyl, aryl,or hydrogen having from 1 to 20 carbon atoms; M is silicon or tin; Z ishalogen, or --Or; b is an integer of from 2 to 4; a is zero, 1, or 2;and the sum of a plus b is equal to 4. The halogen can be fluorine,chlorine, bromine, or iodine. Suitable examples of these coupling agentsinclude silicon tetrahalide, stannic chloride, tetraethylorthosilicate,tetraethoxytin, dimethyldichlorosilane, methyltrichlorosilane,trichlorosilane, methyldichlorosilane, phenyltrimethoxysilane, and thelike. Those compounds in which b is less than 4 are presently consideredto be especially suited for polymerizations initiated with multilithiuminitiators.

Another class of suitable coupling agents are the disilanes which can berepresented by the general formula R_(c) Z_(d) SiSiZ_(d) R_(c) wherein Rand Z are each as defined hereinabove; c is zero or an integer of 1 to2; d is an integer of 1 to 3; and the sum of c + d is equal to 3. Thesedisilane coupling agents include hexahalosilanes such ashexachlorodisilane, or any other of the disilanes containing at leasttwo reactive groups as described and exemplified for the silanes.

It is also within the scope of this invention to employ mixtures of anyof the above suitable coupling agents.

The amount of suitable coupling agent defined above which can beemployed according to my invention can be expressed in terms of theratio of equivalents of the group Z in the coupling agent to lithium inthe initiator employed. Broadly, this ratio of equivalents of Z in thecoupling agent to lithium in the initiator is in the range of from0.01:1 to 1.5:1, preferably 0.25:1 to 1.25:1.

Those coupling agents in which Z is halogen are not considered to besuitable for polymerization systems where random copolymers ofconjugated dienes and vinyl aromatic hydrocarbons are prepared in thepresence of randomizing agents such as potassium alkoxides and the like.However, types of randomizing agents such as ethers, thioethers andtertiary amines, do not render such coupling agents in which Z ishalogen unsuitable for said copolymerizations. If copolymerizationsrandomized with such as potassium alkoxides are conducted according tothis invention, compounds wherein Z is --OR should be employed.

The coupling agent is added in the process of my invention essentiallycontinuously to the polymerization system, commencing afterpolymerization has started. The addition can be conducted substantiallyover any portion of the course of the polymerization reaction,commencing after polymerization of the monomers has been initiated bythe organolithium initiator. Broadly, the addition of the polymerizablecoupling agent can be commenced from a degree of conversion of about 3percent up to and including essentially quantitative conversion ofmonomers. The addition can be ceased at or after essentially completeconversion of monomers, or at any time prior thereto. It is presentlypreferred that the addition be from about 3 percent conversion up toabout 75 percent conversion of monomers to polymer, and more preferablyfrom about 3 percent up to about 30 percent conversion of monomers topolymer. Broadly, it is presently preferred that the addition of thecoupling agent to the polymerization mixture be started before at leastabout 30 percent conversion of monomers to polymer has been obtained. Itis to be realized that intervals to achieve such conversions whenexpressed in terms of elapsed time may, under some conditions, be ofshort duration, since, for example, at high catalyst levels and highpolymerization temperatures, the polymerization rate may be quite rapid.On the other hand, if the polymerization rate is decreased such as bydecreasing the polymerization temperature and/or catalyst level, theduration of time employed in the essentially continuous addition of thepolymerizable coupling agent may range up to several hours.

A feature of my invention lies in the ability to control the molecularweight of the final product by timing the start of the coupling agentaddition. That is, the final molecular weight of the polymer can beadjusted by proper selection of the time period between the start ofpolymerization and the start of the coupling agent addition. Forexample, the longer the delay in the start of the coupling agentaddition after the polymerization has been initiated, the lower will bethe molecular weight of the polymer. Employing usual amounts ofinitiator and polymerization temperatures, polymers in a desirableprocessable Mooney viscosity range can be obtained when a delay in theaddition of from 15 up to 30 seconds is employed after initiation iscommenced before the start of the addition of the non-polymerizablecoupling agent.

POLYMERIZATION SYSTEMS

My invention is applicable to the polymerization of monomers which arepolymerizable with organolithium initiators.

This invention is believed to be particularly valuable for theproduction of rubbery homopolymers such as polybutadiene orbutadiene/styrene copolymers in the normally solid rubbery range, i.e.having a butadiene/styrene ratio of about 60/40 to about 99/1 However,other ratios of monomers may, of course, be employed in preparingcopolymers according to this invention.

The monomers which can be employed in a process according to myinvention are those known to polymerize with lithium initiator systems.Such monomers include the particularly useful conjugated dienes of from4 to 12 carbon atoms per molecule, presently preferred being those offrom 4 to 8 carbon atoms per molecule for commercial availability, andalso the monovinyl-substituted aromatic compounds of from 8 to 20 carbonatoms per molecule, presently preferred being those of from 8 to 12carbon atoms per molecule since more readily commercially available. Ingeneral, I term the polymer products of my invention to be polymers ofconjugated diene, which term is intended to include homopolymers of anyone conjugated diene, copolymers of any two or more conjugated dienes,and copolymers of one or more conjugated dienes with one or moremonovinyl-substituted aromatic compounds.

Examples of suitable monomers include the presently preferred1,3-butadiene, isoprene, and styrene; as well as2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene,2-phenyl-1,3-butadiene, 1-vinylnaphthalene, 3-methylstyrene,4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene,4-tert-butylstyrene, 4-isopropylstyrene, and the like. Mixtures of twoor more monomers can be employed. Furthermore, the monomers can be addedtogether, or in sequential addition and hence sequential polymerizationof different monomers also can be utilized according to the process ofmy invention.

ORGANOLITHIUM INITIATORS

The process of my invention is broadly applicable to any of theorganolithium polymerization initiator systems known in the art topolymerize a polymerizable monomer I have described above.

The term "organolithium initiators" is used in a broad sense to indicateany of the initiators which include one or more lithium atoms and one ormore organic moieties, whether as organolithium compounds, organolithiumadducts, multilithium initiators, and other more or less descriptiveterms.

Organolithium polymerization initiators useful in the context of myinvention include those which can be represented by the formula R'Li_(y)wherein R' is a hydrocarbyl radical having a valence equal to the valueof y, with y being an integer of from 1 to 4. The hydrocarbyl radical R'generally is limited to about 20 carbon atoms in practice, althoughhigher molecular weight compounds can be utilized. Exemplary initiatorsinclude methyllithium, n-butyllithium, sec-butyllithium, n-decyllithium,phenyllithium, 1-naphthyllithium, p-tolyllithium, cyclohexyllithium, andothers known to the art wherein R' is an aliphatic, cycloaliphatic,aromatic, or combination radical with a suitable valence and lithium issubstituted in from 1 to 4 positions as indicated by the generalformula.

Adducts of lithium metal with condensed ring aromatic hydrocarbons suchas naphthalene, anthracene, and the like, are suitable initiators. As isknown in the lithium initiator art, such adducts can be solubilized ifdesired, with the use of a small amount of a polymerizable monomer intheir preparation.

Various reaction products of organomonolithium compounds with compoundssuch as the polyvinyl-substituted aromatic compounds such asdivinylbenzene, substituted vinyl products such as diisopropenylbenzene,and with various polyvinyl-substituted compounds of silicon orphosphorus such as tetravinylsilane or trivinylphosphine, can beutilized. These initiators can be solubilized if desired by the use of asmall amount of a polymerizable monomer by contacting therewith thecomplex initiator so formed or prepared. Presently preferred areinitiators formed from such as n-butyllithium and divinylbenzene.

In order to obtain the advantages of this invention, it may be necessaryto employ slightly higher levels of initiator than those conventionallyemployed in polymerizations with organolithium initiators in thepreparation of normally solid rubbery polymers. Broadly, the amount ofinitiator employed according to this invention can range from about 0.2to 100 milliequivalents of lithium in the initiator, presentlypreferably from 0.5 to 15, milliequivalents of lithium in the initiatorper hundred grams of monomer employed.

POLYMERIZATION CONDITIONS

Polymerization conditions such as temperatures and times are thoseconventionally employed in the art. Pressures employed are thosesufficient to maintain the polymerization mixture in the liquid phase.Diluents are generally employed as is known in the prior art inpolymerizations employing organolithium initiators. Suitable diluentsinclude hydrocarbons having from 4 to 12 carbon atoms per molecule suchas n-butane, n-hexane, n-octane, n-dodecane, toluene, benzene,cyclohexane and the like. Mixtures of said suitable diluents can beemployed if so desired. Copolymerizations, as indicated above, may becarried out in the presence of compounds known to be randomizers. Thesecompounds are polar materials which have been mentioned earlier such asethers, thioethers, and tertiary amines along with the alkali metalalkoxides such as potassium alkoxide or other similar compounds known inthe prior art.

Typical polymerization reaction conditions can include any conditiongenerally known to the art for polymerization of monomers as describedwith initiators as described. For example, and illustrative only, arepolymerization temperatures varying over a broad range which isgenerally from about -100° to +300° F., from a polymerization time of afew minutes to upwards of 48 hours or more as may be desired orconvenient for commercial practice.

Recovery of the polymer from polymerization mixtures of this inventionis also by conventional processes. The polymerization is generallyterminated or shortstopped with a material which inactivates or destroysthe organolithium initiator such as alcohols or acids, water and thelike. The polymerization mixture is then generally admixed with astabilizer, e.g., antioxidants and the like. The polymer, havingstabilizer incorporated therein, is then recovered by conventional meanssuch as steam stripping of the polymerization mixture or coagulation ofthe polymer solution with a non-solvent such as isopropyl alcohol.

Shown below in Table I is a list of presently preferred polymerizationsystems in which my invention provides polymers of improvedprocessability.

                  Table I                                                         ______________________________________                                                            Coupling                                                  Initiator Monomer(s)                                                                              Agent      Randomizer                                     ______________________________________                                        n-Butyllithium                                                                          Butadiene/                                                                              Silicon    Tetrahydrofuran                                          Styrene   tetrachloride                                             n-Butyllithium                                                                          Butadiene/                                                                              Tetraethyl-                                                                              Tetrahydrofuran                                                    orthosilicate                                             n-Butyllithium                                                                          Butadiene/                                                                              Stannic    Tetrahydrofuran                                          Styrene   chloride                                                  n-Butyllithium                                                                          Butadiene Silicon    None                                                               tetrachloride                                             Multilithium.sup.(a)                                                                    Butadiene Silicon    None                                                               tetrachloride                                             Multilithium.sup.(a)                                                                    Butadiene/                                                                              Silicon    Tetrahydrofuran                                          Styrene   tetrachloride                                             Multilithium.sup.(a)                                                                    Butadiene/                                                                              Tetraethyl-                                                                              Potassium-                                               Styrene   orthosilicate                                                                            tertiary-                                                                     amyloxide                                      Multilithium.sup.(a)                                                                    Isoprene/ Silicon    Tetrahydrofuran                                          Styrene   tetrachloride                                             Multilithium.sup.(a)                                                                    Isoprene/ Tetraethyl-                                                                              Potassium-                                               Styrene   orthosilicate                                                                            tertiary-                                                                     amyloxide                                      ______________________________________                                         .sup.(a) Prepared from such as n-butyllithium and divinylbenzene.        

EXAMPLES

The following examples are intended to be illustrative of my invention,particular species employed, particular reaction conditions, particularratios, are to be considered as illustrative and not as limitative ofthe scope of my invention.

EXAMPLE I

Butadiene and styrene were used to prepare a series of copolymersaccording to the following recipe:

    ______________________________________                                        Polymerization Recipe                                                                          Parts, by wt. or (mhm)                                       ______________________________________                                        1,3-Butadiene      75                                                         Styrene            25                                                         Cyclohexane        760                                                        Tetrahydrofuran (THF)                                                                            1.5                                                        n-Butyllithium, mhm                                                                              (2.0)                                                      Silicon Tetrachloride (SiCl.sub.4)                                                               (0.525)                                                    Temperature, ° C..sup.(a)                                                                  70-101                                                    Time, minutes      10-15                                                      ______________________________________                                         .sup.(a) Initiation temperature to peak temperature.                          Charge Orders:                                                                Cyclohexane, N.sub.2 purge, butadiene, styrene, THF, heat to initiation       temperature (70° C.), n-BuLi, SiCl.sub.4 added continuously over a     1.0 minute period after a delay of 0.25 minute following the n-BuLi           addition.                                                                

At the end of the polymerization period the polymer from each run wasisolated by steam stripping in the presence of 0.5 part by weight per100 parts by weight of monomers of an antioxidant,2,2'-methylenebis(4-methyl-6-tert-butylphenol).

Run A: Six polymers were obtained using the above recipe. Theseexhibited Mooney viscosities in the range of 114 to 125 ML-4 at 212° F.The polymers from these runs were dissolved in cyclohexane, mixed with37.5 parts by weight of extender oil (Philrich* 5) and the solutionscombined. The combined oil-rubber solution then was steam stripped torecover the oil extended polymer.

Run B: Another run was made utilizing the same polymerization recipe asdescribed above, the same Si:Li stoichiometry, and the same catalystlevel as shown in the recipe. However, in this control run, anonpolymerizable coupling agent, silicon tetrachloride, was added insubstantially one portion after 10 minutes of polymerization. Thepolymerization was initiated at 70° C., peaked at 108° C. at about 2.5minutes after initiation. The reaction mixture was stirred for 20minutes additional at about 90° C. The polymer then was recovered asdescribed for the runs above. Monomer conversion was 100 percent, butthe Mooney viscosity of the recovered polymer was only 30 ML-4 at 212°F., as compared with values of 114 to 125 for the unextended polymersmade by the procedure of the invention. The control polymer, designatedRun B, thus obviously was not suitable for oil extension and processingevaluation of an oil extended polymer simply could not be accomplished.

For the combined runs of the invention (Run A), the compounding recipeemployed is shown as follows:

    ______________________________________                                        Compounding Recipe                                                                                 Parts                                                    ______________________________________                                        Rubber.sup.1           137.5                                                  Carbon Black.sup.2     40                                                     Zinc Oxide             3                                                      Stearic Acid           2                                                      Santoflex AW.sup.3     1                                                      Sunoco 3425 Wax.sup.4  2                                                      ______________________________________                                         .sup.1 Extended with 37.5 phr highly aromatic oil of type 101 under ASTM      D2226-63T.                                                                    .sup.2 Type N 220 under ASTM D2516-66T.                                       .sup.3 Condensation product of n-phenetidine and acetone.                     .sup.4 Paraffin wax processing oil, sp. gr. 0.906, m.p. about 128°     F.                                                                       

Further polymers were prepared employing a polymerization recipe asdescribed below:

    ______________________________________                                        Polymerization Recipe                                                                          Parts, by wt. or (mhm)                                       ______________________________________                                        1,3-Butadiene      75                                                         Styrene            25                                                         Cyclohexane        760                                                        Tetrahydrofuran (THF)                                                                            1.5                                                        n-Butyllithium, mhm                                                                              (0.55)                                                     Silicon tetrachloride, mhm                                                                       (.145)                                                     Temperature, ° C..sup.(a)                                                                 70                                                         Time, minutes.sup.(b)                                                                            30                                                         ______________________________________                                         .sup.(a) Initiation temperature.                                              .sup.(b) Polymerization time only.                                            Charge Order:                                                                 Cyclohexane, N.sub.2 purge, butadiene, styrene, THF, heat to 70°       C., H-BuLi, polymerize 30 minutes, SiCl.sub.4, react for 30 minutes.     

The coupling agent, here silicon tetrachloride, was added as a singleportion and only after essentially complete conversion of the monomersto polymer had been obtained. Five separate runs were made, with polymerfrom each recovered as described hereinabove. The five polymers thusprepared by employing terminal single-portion addition of coupling agentexhibited Mooney viscosity values ranging from 116 to 129 ML-4 at 212°F. These five polymers were oil extended, blended together, and thencompounded in the recipe as described above for previous runs. Thecombined product was termed Run C. The Mooney ML-4 at 212° F. of theoil-extended polymer of Run C was 51. This control polymer Run C thenwas evaluated along with two other control polymers in a processingevaluation comparison with processing results as shown below;

                                      Table II                                    __________________________________________________________________________                         Band   Extrusion                                                                          at 250° F.                                       Raw  Band/.sup.(a)                                                                      Rating.sup.(b)                                                                       Garvey                                                                             Feed                                         Polymer    Mooney                                                                             Bank 195° /158° F.                                                          Rating.sup.(c)                                                                     Rating.sup.(d)                               __________________________________________________________________________    Run A -- Invention                                                                       55   TR   8/10   9    6                                            Run C -- Control                                                                         51   LT-RF                                                                              2 LT/2 9    7                                            Solution SBR.sup.(e) -                                                        Control    46   LT-F 2 LT/4 8    8                                            SBR-1712.sup.(f)                                                                         47   TR   8/10    9-  9                                            __________________________________________________________________________     .sup.(a) Milling observations:                                                LT = loose on top; RF = rolling folding bank; F = folding bank; TR = tigh     band with rolling bank.                                                       .sup.(b) Rating: 10 best.                                                     .sup.(c) Rating: 12 best.                                                     .sup.(d) Rating: 10 best.                                                     .sup.(e) Commercially available solution polymerized butadiene/styrene        75/25 copolymer made with organolithium initiator and extended with 37.5      phr highly aromatic oil as indicated in the compounding recipe.               .sup.(f) Commercially available emulsion polymerized butadiene/styrene        75/12 copolymer prepared according to ASTM Method D-1419-61T.            

These results clearly show that terminal addition of silicontetrachloride in the preparation of the oil extended solutionpolymerized copolymers gave essentially no improvement in processing.The results shown hereinabove for Run A of the invention show the markedimprovement of polymer processing achieved according to the invention.Comparison of Run A properties with the emulsion polymerized SBR showthat it is now possible to produce, as I have discovered, solutionpolymerized polymers with properties equal to or better than theconventionally but more expensively and difficultly produced emulsionpolymerized polymers.

EXAMPLE II

Random butadiene/styrene 75/25 copolymers were prepared by thecontinuous addition of initiator as well as the continuous addition ofcoupling agent, simultaneously. Such process produces polymers withbroad molecular weight distributions and highly desirable processingcharacteristics.

    ______________________________________                                        Polymerization Recipe                                                                              Parts                                                    ______________________________________                                        Butadiene              75                                                     Styrene                25                                                     Cyclohexane            760                                                    Tetrahydrofuran        1.5                                                    n-Butyllithium         Variable                                               Silicon Tetrachloride  Variable                                               Temperature, ° F.                                                                             Adiabatic                                              Time, minutes          Variable                                               ______________________________________                                    

Solvent, monomer, and randomizing agent (THF) were charged to thereactor, the solution then heated to about 158° F. Small amounts ofinitiator were added in increments until the scavenger level was reachedas indicated by a slight heat rise. Thereupon, addition of bothn-butyllithium and silicon tetrachloride was commenced immediately andcontinued under adiabatic conditions for several minutes to insurequantitative conversion. The polymer solution was mixed with anisopropyl alcohol/toluene solution of an antioxidant2,2-methylene-bis(4-methyl-7-tert-butylphenol) and steam stripped toremove solvent.

Test results on the polymers so prepared are as follows:

                  Table III                                                       ______________________________________                                                   D      E        F        G                                         ______________________________________                                        BuLi, part (mmoles)                                                                        0.099    0.096    0.096  0.096                                                (1.55)   (1.50)   (1.50) (1.50)                                  SiCl.sub.4, part (mmole)                                                                   0.0626   0.0605   0.0605 0.0605                                               (0.368)  (0.356)  (0.356)                                                                              (0.356)                                 Time of addn, minutes                                                                      7.75     10.0     5.0    2.5                                     Conv. at end of addn, %                                                                    --       87       60     39.sup.(a)                              Temperature, ° F                                                       initial      161      165      162    164                                     peak         195      200      190    192                                     Polymerization time,                                                          min.         14       15       18.5   20                                      Conversion, %                                                                              100      100      100    100                                     Inherent viscosity.sup.(b)                                                                 1.75     2.22     1.97   2.31                                    Mooney, ML-4.sup.(c)                                                                       77.5     100      102    127                                     Mooney Relaxation.sup.(d)                                                                  0.15     0.21     0.17   0.22                                    Mw × 10.sup.-3.spsp.(c)                                                 Mn × 10.sup.-3                                                                       268/143  367/164  321/194                                                                              397/190                                 HI           1.9      2.2      1.6    2.1                                     ______________________________________                                         .sup.(a) Conversion at 3.0 minutes.                                           .sup.(b) Determined according to the procedure of U.S. 3,278,508, Col. 20     notes a and b.                                                                .sup.(c) ASTM D 1646-63.                                                      .sup.(d) Ratio of Mooney value obtained 30 sec. after rotor on machine is     turned off to that value obtained at the instant the rotor is turned off      after the normal 4 minute run time.                                           .sup.(e) Heterogeneity Index (HI) is defined as the ratio of the weight       average molecular weight (Mw) to the number average molecular weight (Mn)     as determined by gel permeation chromatography.                          

The addition simultaneously of both the initiator and the coupling agentwould appear at first to be self-defeating since it would be expectedthat termination would occur almost before initiation could start.Nevertheless, the results above show desirable molecular weights,molecular weight distribution, desirable heterogeneity index (HI)values. A relatively high degree of branching in the polymer prepared bythe invention is indicated by the Mooney relaxation values which arerelatively high for butyllithium initiated polymers.

Polymers prepared according to the process of my invention show improvedprocessability over those prepared according to the prior art. Inparticular, this improvement is seen in the milling of rubbery polymersat about 195° F., wherein the polymers of my invention show much bettermilling behavior than control polymers made according to the prior art.In addition, my polymers also exhibit significantly higher greenstrength compared to the polymers of the prior art. My polymers alsoexhibit low die swell and shrinkage on extrusion and thesecharacteristics are valuable in applications which employ molding of therubbery product. Another characteristic of the polymers of my invention,is the low viscosity of a hydrocarbon solution of polybutadiene such asa solution in styrene.

The polymers of this invention which are normally solid rubbery polymerscan be compounded with conventional fillers, stabilizers, curatives,vulcanization accelerators, plasticizers, pigments, and the like whichare conventionally employed in the rubber compounding art. Thesepolymers can be used in applications where natural rubber and thesynthetic rubber such as SBR have been employed heretofore such as inthe manufacture of tires, tubing, belting, gaskets, hose and the like.

I claim:
 1. In a process for the polymerization of at least onepolymerizable monomer comprising a polymerizable conjugated diene,polymerizable monovinyl-substituted aromatic compound, or both, underpolymerization conditions with an organolithium initiator, theimprovement which comprises initiating the polymerization reaction withsaid organolithium initiator and adding said organolithium initiator ina continuous manner, further adding at least one nonpolymerizablesilicon or tin coupling agent in a continuous manner commencing from adegree of conversion of about 3 percent up to about 75 percent, suchthat each of said organolithium initiator and said nonpolymerizablecoupling agent is added essentially continuously simultaneously duringat least a portion of the course of said polymerization.
 2. The processaccording to claim 1 wherein said adding of said nonpolymerizablecoupling agent extends up to about 75 percent conversion of saidmonomer.
 3. The process according to claim 1 wherein said organolithiuminitiator and said nonpolymerizable coupling agent are each addedessentially continuously over the course of the polymerization reaction.4. A process according to claim 1 wherein said nonpolymerizable siliconor tin coupling agent is represented by the general formulae R_(a)MZ_(b) or R_(c) Z_(d) Si--SiZ_(d) R_(c) wherein each R is a hydrocarbylradical of 1 to 20 carbon atoms per molecule or hydrogen; M is Si or Sn;Z is halogen, or --OR; b is an integer of 2 to 4, and a is 0, 1, or 2,such that a plus b is equal to 4; said halogen is fluorine, chlorine,bromine, or iodine; and c is 0, 1, or 2, and d is 1, 2, or 3, such thatc plus d is equal to
 3. 5. The process according to claim 1 wherein saidcoupling agent is a silicon tetrahalide or tetraalkyl orthosilicate. 6.In a process for the polymerization of at least one polymerizablemonomer comprising a polymerizable conjugated diene, polymerizablemonovinyl-substituted aromatic compound, or both, under polymerizationconditions with an organolithium initiator, the improvement whichcomprises adding the said organolithium initiator essentiallycontinuously to the polymerization reaction system and further adding tothe polymerization reaction system at least one nonpolymerizable siliconor tin coupling agent essentially continuously during at least a portionof the course of said polymerization, wherein the addition of saidnonpolymerizable coupling agent is commenced within about 3 percent upto about 75 percent monomer conversion and such that the addition ofsaid organolithium initiator and said coupling agent are each conductedat least in part simultaneously with the other, thereby preparing apolymer of improved processability.
 7. A process according to claim 6wherein said polymerizable conjugated diene contains 4 to 12 carbonatoms per molecule, and said monovinyl-substituted aromatic compoundcontains 8 to 20 carbon atoms per molecule.
 8. The process according toclaim 6 wherein said adding of said nonpolymerizable coupling agentcontinues up to essentially complete monomer conversion.
 9. The processaccording to claim 6 wherein said adding of said nonpolymerizablecoupling agent extends up to about 75 percent conversion of saidmonomer.
 10. The process according to claim 6 wherein said adding ofsaid nonpolymerizable coupling agent extends from after about 3 percentconversion up to about 30 percent conversion of said monomers.
 11. Theprocess according to claim 6 wherein said adding of saidnonpolymerizable coupling agent extends from about 3 percent conversionup to about 75 percent conversion.
 12. The process according to claim 2wherein said nonpolymerizable silicon or tin coupling agent isrepresented by the general formulae R_(a) MZ_(b) or R_(c) Z_(d)Si--SiZ_(d) R_(c) wherein each R is a hydrocarbyl radical of 1 to 20carbon atoms per molecule or hydrogen; M is Si or Sn; Z is halogen, or--OR; b is an integer of 2 to 4, a is 0, 1, or 2, such that a plus b isequal to 4; said halogen is fluorine, chlorine, bromine, or iodine; c is0, 1, or 2; d is 1, 2, or 3; such that c plus d is equal to
 3. 13. Theprocess according to claim 12 wherein is employed a ratio of equivalentsof Z in said couling agent to lithium in said organolithium initiator ofabout 0.01:1 to 1.5:1.
 14. The process according to claim 13 whereinsaid organolithium initiator is employed in an amount sufficient toprovide about 0.2 to 100 milliequivalents of lithium in said initiatorper 100 grams of said polymerizable monomer employed.
 15. The processaccording to claim 14 further employing a randomizer during saidpolymerization reaction, and said randomizer is a polar material and isan ether, thioether, tertiary amine, or alkali metal alkoxide.
 16. Theprocess according to claim 15 wherein said coupling agent is said R_(a)MZ_(b).
 17. The process according to claim 16 wherein said couplingagent is a silicon tetrahalide or tetraalkyl orthosilicate.
 18. Theprocess according to claim 17 wherein said coupling agent is a silicontetrahalide.
 19. The process according to claim 18 wherein saidpolymerizable monomer is a conjugated diene and is butadiene; saidorganolithium initiator is n-butyllithium; and said coupling agent issilicon tetrachloride.
 20. The process according to claim 18 whereinsaid polymerizable monomer is butadiene and styrene, the resultingpolymer is a butadiene/styrene copolymer, said organolithium initiatoris n-butyllithium; and said coupling agent is silicon tetrachloride. 21.The process according to claim 18 further employing a randomizer whereinsaid randomizer is tetrahydrofuran, said polymerizable monomer isbutadiene and styrene or is isoprene and styrene, said coupling agent issilicon tetrachloride, and said initiator is n-butyllithium or is amultilithium composition prepared from n-butyllithium anddivinylbenzene.
 22. The process according to claim 17 further employinga randomizer wherein said randomizer is tetrahydrofuran or potassiumtert-amyloxide, said polymerizable monomer is butadiene and styrene oris isoprene and styrene, said coupling agent is silicon tetrachloridewhen said randomizer is tetrahydrofuran, or tetraethyl orthosilicatewhen said randomizer is potassium tert-amyloxide and said initiator isn-butyllithium or is a multilithium composition prepared fromn-butyllithium and divinylbenzene.
 23. In a process for thepolymerization of at least one polymerizable monomer with anorganolithium initiator, the improvement comprising initiating saidpolymerization with a minor portion of said organlithium initiator andcontinuing the addition thereof substantially continuously, adding tothe polymerization reaction system commencing after at least about 3percent monomer conversion up to about 75 percent conversion at leastone nonpolymerizable coupling agent, simultaneously with the remainderof said organolithium initiator and essentially continuously during atleast a portion of the remaining course of saidpolymerization,continuing said polymerization to substantially completemonomer conversion, and shortstopping said polymerization, wherein saidpolymerizable monomer is at least one polymerizable conjugated diene, atleast one polymerizable monovinyl-substituted aromatic compound, orboth, and wherein said nonpolymerizable couping agent is represented bythe general formulae R_(a) MZ_(b) or R_(c) Z_(d) Si--SiZ_(d) R_(c)wherein each R is a hydrocarbyl radical of from 1 to 20 carbon atoms permolecule or hydrogen; M is Si or Sn; Z is halogen, or --OR; a is 0, 1,or 2, b is 2, 3, or 4, such that a plus b is equal to 4; said halogen isfluorine, chlorine, bromine, or iodine; c is 0, 1, or 2, d is 1, 2, or3, such that c plus d is equal to
 3. 24. In a process for thepolymerization of at least one polymerizable monomer comprising apolymerizable conjugated diene, polymerizable monovinyl-substitutedaromatic compound, or both, under polymerization conditions with anorganolithium initiator, the improvement which comprises commencingpolymerization with said initiator, adding both said organolithiuminitiator and at least one nonpolymerizable silicon or tin couplingagent simultaneously and at least in part essentially continuouslyduring at least a portion of the course of said polymerization, therebypreparing a polymer of improved processability.
 25. A polymerizationprocess for the polymerization of at least one polymerizable monomerunder polymerization conditions with an organolithium initiator, thesteps comprisingcommencing polymerization of said monomer with anorganolithium polymerization initiator wherein said organolithiumpolymerization initiator is added essentially continuously substantiallyover the course of the polymerization reaction, further addingessentially continuously and commencing substantially simultaneouslywith the initiator to the polymerization reaction commencingsubstantially with initiation at least one nonpolymerizable couplingagent essentially continuously during at least a portion of the courseof said polymerization and at least in part simultaneously with saidorganolithium initiator, polymerizing to substantially complete monomerconversion, and shortstopping said polymerization, wherein saidpolymerizable monomer is at least one polymerizable conjugated diene, atleast one polymerizable monovinyl-substituted aromatic compound, orboth; wherein said nonpolymerizable coupling agent can be represented bythe general formulae R_(a) MZ_(b) or R_(c) Z_(d) Si--SiZ_(d) R_(c)wherein each R is a hydrocarbyl radical of from 1 to 20 carbon atoms permolecule or hydrogen; M is Si or Sn; Z is halogen, or --OR; a is 0, 1,or 2, b is 2, 3, or 4, such that a plus b is equal to 4; said halogen isfluorine, chlorine, bromine or iodine; c is 0, 1, or 2, d is 1, 2, or 3,such that c plus d is equal to
 3. 26. In a process for thepolymerization of at least one polymerizable monomer with anorganolithium initiator, the improvement which comprises adding saidorganolithium initiator and simultaneously at least one nonpolymerizablecoupling agent essentially continuously substantially during the courseof said polymerization to substantially complete monomer conversion, andshortstopping said polymerization, wherein said polymerizable monomer isat least one polymerizable conjugated diene, at least one polymerizablemonovinyl-substituted aromatic compound, or both;wherein saidnonpolymerizable coupling agent can be represented by the generalformulae R_(a) MZ_(b) or R_(c) Z_(d) Si--SiZ_(d) R_(c) wherein each R isa hydrocarbyl radical of from 1 to 20 carbon atoms per molecule orhydrogen; M is Si or Sn; Z is halogen, or --OR; a is 0, 1, or 2, b is 2,3, or 4, such that a plus b is equal to 4; said halogen is fluorine,chlorine, bromine, or iodine; c is 0, 1, or 2, d is 1, 2, or 3, suchthat c plus d is equal to 3.